Cutting oil composition



U i d S e Patcm Ofiicct Refining Company, New York, .ofMaine a No Drawing.

Amos Dorinson, fl'ark Forest, lll.',: assignor 'Y., ,ac orp oration Serial 5N0; 394,499 g 4 claims; c ass-r 333 1 n My inventionrelatesto cuttingoil compositions containing sulfur-chlorinatedpinene type additives and particularly to the use'of basic barium mahogany petroleum sulfonate to inhibit'corrosion caused by and formation of turbidity in such cutting oil compositio 1 Mineral oil compositions containing sulfur-chlorinate pinene type additives, for example, sulfur-chlorinated al-' pha-pinene,,are Widely used as cutting oilsin metal-work ing processes. It has been found that oil solutions ofsuch additives up to a concentrationofab'out' 2-;per cent will not stain copper and such solutions are used as cutting oils for copper and copper alloys as well as for, ferrous metals; In the working of ferrous metals with' such compositions, however, it is often observed that the workpiece acquires'a brown stain and that the slideways and other exposed parts of the machine become similarly stained. Furthermore, when solutions of these additives in petroleum oils, especially in solvent-refined oils,*standtions and undesirable appearance.

for a period of time, they become turbid, giving the'so lu- I have found that the staining" of ferrous metals' caused by the corrosive action of cutting oil compositions con'-' taining sulfur-chlorinated pinene type additives and the occurrence of turbidity in such compositions can be inhibited eifectively or evensuppressed'entirely'by theaddition of basic barium mahogany petroleum sulfonate to the composition. Moreover, I have found that basic barium mahogany sulfonate'surprisingly'is superior to other oilsoluble mahogany sulfonate soapssuch as sodium, neu-- tral barium or basiccalciuin soaps when compared either on the basis of the total sulfonate"content or, for the basic soaps, on the basis of reserve alkalinityji*The'basic barium sulfonate is effective at lower concentrations and for longer periods of time than sodium, neutral barium or: calcium sulfonate. Surprisingly, the advantageszof basic barium sulfonateare peculiar to it and donotres'ide' separately in eitherthe barium sulfonate orthe basicity of the excess alkaline earthhydroxide." Thus, invention provides advantageous cutting oil compositions contain ing sulfur-chlorinated pinene type additives' which are remain substantially clear on standing. a

substantially nonkor'rosivt'o ferrous metals and which' By a basic'barium- 'mahoga'ny petroleum"sulfoiiate," I 7 mean a barium sulfonate derived from the oil-soluble or mahogany petroleum acids'bb'tiained by sulfuric'acid, ole um or sulfur trioxide treatment. of petroleum oilsiand cori- I taining barium hydroxide in 'excess ofthatrequired fori neutralization of the acids.- Thebasic barium mahogany}; sulfonate advantageously is prepared by treating a petro-- I leum oil with oleum or sulfurtrioxide, separating the sludge and neutralizing the oil-Isollible mahogany acids,

i. e. the acid oil, with ammonia, concentrating the re suiting ammonium sulfonate by. isopropyf alcohol treat ment and converting the ammonium sulfonate tobasicf' barium sulfonate bytreatmentwithexcess barium-by droxide. Alternatively, 'the basiob ariiim sulfonate may be prepared by directly neutralizing aisludgefree abi es with excess ba rimh'fiydioxidflf V I 9 '10 jgany sulfonate. a; acuttlngfbil composit By sulfur chlorinated ipin'ene type additive," I. ifnean;

a' sulfur-chlorinated'pinenle o tatty {compounds such as fatty esters ,or fatty acids example, ,suitab1e f additives include sulfur-chi 5 e. g. with-sulfur" ,nionochloride; falph" oil fatty acids According to sufiicieritto inhi tithe' co o iveness urbi ty. of. composition. "."G'enerally; about 0.03 .gcentofbasicbariumsulfonate based, 7 isasuflieient and "at least about 0.06;. per 'centfis pret v a. sulfur-chlorinated: pinerie ltype; additive 1 i considerations will'fl'generally preclude theus than bout 0.6 per, cent o f lthebasic bari The sulfonate '1 I 20. r a a i a t i a l i mntr sns o fli l -l the ingredient. lforexamplegabout to 1.0.per; cent 1 of e60; perlcentfbasiobarium 'sulfonate. concentrated preparation or: about 11.2 to'4.0 per cent of: a 15 pe dilute preparation is added -to the. composition;- Th resulting comp ositio'nis siubst rousmetals and can be used; in 'intal-working] proc worked or the; I K o H Moreover,-; the formation or; turbidity in such ,c'o'

a0: tions: issubstantially; inhibited, and, a desirable appe ance pp 'tio'n stands forlong periods isrkepteven when th" 1 My invention will be" further-illustrated b refe to the followingfexari pl a V I aaaapz a V The" corrosivenfess "of mineral oili c'orn osition ing a'sulfur-chlorinated mixture of -*a'lpl a"p 40 such compositioscontaining basic' barium sulfon'at sodium sulfonate was evaluated.

The tests were car!" d (A181 1018) 'whichfwer em air and lfinallyiiot r ulf 'r-chlorinated pine ne type addi tives manifests itselfb eithercompletely-suppressing or, A o on of staining of 'the steel panel; theadditiye and by etai i .Iherateof--growth of ja onceiit. asforrne d; .Bot h flofr stained. spot on the 1 panel these facto and inla' t'rfora'few with a dense, 'rriatteg-brow (a? sol'ventfrefined tiiien treated, ,naphthenicyCoastal oil.

Patented l une 19 a or mixtures of i pinene {and I ine'n'e; sulfurchlorinated mixtures-of alpha-pinen'e;and 'oleiegacidfoi. sulfur-chlorinated;alpha p'ii ene and .ni t iiylie e'rs or lard Largerain'ountso sulfonate niay be' used, but conom c without undesirable stainin'gfofflith metalpiece 1pm Q metal parts of hc working machineif .v an methyl esters o f flard oil 'fatty acids additive ncludingl gioii. ut on" mild se1fiban1s rface' ground on both sides,

bout half g t e -te'stif effects of prolongedfi fli j tsion, of

ni stainingandi s the entire jpanel ii covered,

, a'r'nish, Thelonset f t rnish;

tends to occur sooner a d to-progress motesrapidly in oil" than" "in {an and The basic barium sulfonate preparation used in the tests was prepared by subjecting a solvent-treated Mid- Continent oil, having a viscosity of 200 Saybolt Universal seconds at 100 F. and a viscosity index of 85, to the action of five 25 pound portions of 25 percent 'ol'eum per barrel of oil. After separation of the sludge, the acid oil was blown with air to purge it of sulfur dioxide and neu tral'ized with ammonia. The resulting ammonium sulfonate 'was concentrated by treatment with isopropanol and the concentrated ammonium sulfonate was converted to basic barium sulfonate by treatment with an excess of barium hydroxide. The preparation contained 62.1 per cent basic barium sulfonate, comprising 53 per cent barium sulfonate and 9.1 per cent barium hydroxide. The sodium sulfonate preparation was Petronate, a commercially available sodiumfpetrol'eum sulfonate containing about"60 per cent sodium sulfonate. The per cent inhibitor, i. e. basic barium or sodium sulfonate, used in the tests in this example and in the'following examples refers to the weight per cent of gross preparation, not the net concentration of the active ingredient therein.

The sultur-chlorinated pinene type additive was a sulfur-chlorinated mixture of alpha-pinene and methyl esters of lard oil fatty acids which contained 38 to 4'1 per cent alpha-pinene, 38 to 41 per cent methyl esters of lard oil fatty acids, 9 to 12 per cent sulfur and 9 to 12' per cent chlorine.

When 2 per cent of the sulfur-chlorinated additive in a solvent-refined Mid-Continent oil and no inhibitor was used in the test, the steel panel first showed a stain at 15 days and a strong stain after 60' days. When basic barium sulfonate was added to the above composition in concentrations of 0.1, 0.2 and 0.5 per cent, no stains appeared and the steel' panel remained clean and bright after 60 days. With the same oil containing l'per cent of the additive and no inhibitor, the steel panel first showed. a stain at 15 days and a strong stain after 60 days. When basic barium sulfonate was added'to the above composition in concentrations of 0.1, 0.2 and 0.5 per cent, no stains appeared and the steel panel remained clean and bright after 60' days. I

When a composition of an acid-treated Coastal oil and 2' per cent of the sulfur-chlorinated additive and no inhibitor was used, the steel panel first showed a stain at 21 days and a strong stain after 60 days. When basic barium sulfonate was added to the above composition in a con centration of 0.05 per cent, a stain did not appear on the. steel panel. for 56 days and only scattered. patches. were observed after 60 days, and with concentrations of -1 an dQOLZ- per cent, no stains appeared and the steel panel remained clean and bright after 60 days. With the same oil containing. 1 per cent of the additive and nov inhibitor, the steel panel first showed a stain at 31 days and a strong stain after 60' days. When basic barium sulfonate was added to the'above composition in. concentrations of 0.05,. 0.1 and 0.2 per cent, no stain appeared and the steel panel remained clean and bright after 60 days.

On the other hand, the solvent-refined Mid-Continent oil containing 2 per cent of the sulfur-chlorinated additive and sodium sulfonat'e in, a concentration of 0 .05 percent first showed a stain after days, in 0.1 per cent after 1.7 days, in 0.2 per cent after 24 days, in 0.5 per centiafter 31' days and in lv per centafter 41' days. A strong stain was present on the panel after 60 days at all these concentrations. When a I per cent concentration oi? the additive was. used and 0.05 per cent sodium sulfonate,v a stain appeared'after 52 days and was fairly strong afier 60 days,. at 0.1 per cent concentration a weak stain appearedafteir 60. days, at 0.2 per cent concentration the panel. was cleanv and brightafter 60' days, at0.5'per cent concentrationthe panel stained" at 52 days and" had stained patches after 60 days and at 1 per cent concentration the panel was clean and'bright after 60 days.

The results clearlyindicate that whether. the base oil is a solvent-refined Mid-Continent or. an acid-treated.

Coastal oil and whether the sulfur-chlorinated pinene type additive is" present at a 2 per cent or 1 percent concentration, at concentrations of 0.1 per cent the basic barium sulfonate preparation is an efiective inhibitor of staining while at the same concentration, the sodium sulfonate preparation is not efiective... Moreover, there is an indication that the basic barium 'sulfonate can be efiective at concentrations as low as 0.051 per cent. Comparison of the two preparations on an equimolar basis, each weight per cent of'basicbarium sulfona'te' being equivalent to; 0:7 7 per cent sodium sulfonate, shows the superiority of the basic barium sulfonate in an even more pronounced manner.

Example Il The corrosiveness of mineraloil compositions containing a sulfur-chlorinated alpha-pinene additive including such compositions containing the basic barium sulfonate of Example Iwas also evaluated according. to the procedure of Example I. The additive contained 64 to per cent alphapin'ene, 15 to 18 per cent sulfur and 15 to 1-8 per cent chlorine.

When a mineral oil composition containing. the additive in a concentration of 1.08 per cent and no inhibitor was used in the-test, the steel panel first showed a stain after 1.3 days and was lightly stained after 30 days. When basic barium sulfonate in a concentration of 0.1- per cent was added to the above composition, a stain appeared on the steel panel after. 1-3 days but no more than a few stained patches were observed after 30 days. With a concentration of 0.54 per cent of the additive and no inhibitor, a stain appeared after 13 days and the steel panel was sparsely stained after 30 days. Whenbasic barium sulfonate was added to the composition in a concentration of 0.1 per cent, a stain appeared after 1 3 daysbut only a few stained patches were observed after 30 days.

The results indicate growth of the stain is definitely slowed down.

Example III The corrosiveness of mineral oil compositions containing a sulfur-chlorinated mixture of alpha-pinene and oleieacid'additive including such compositions containing the basic barium sulfonate of Example I- was evaluated according to the. procedure of Example I. The additive contained 3 8 to. 4-1 per cent alpha-pinene, 38 to 41 per cent oleic acid, 9. to 12 per cent sultur, and 9 to 12 per cent chlorine;

Whena mineraloil composition containing the additive in a concentration of 2 per cent and noinhibitor was used in the test, the steel panel showed a stain after 13 daysand a str ong stain after 30 days. When basic barium" The: results.- show that compositions containing sulfurchlorinated: mixtures of alpha-pinene and oleic acid can berendered entirely non-staining, by the. addition of. 0.1 per cent basic barium sulfonate. v

Example IV The. corrosivenessof mineral oil compositions contain.-

ing the sulfur-chlorinated mixture of. alpha-pinene. and

methyl esters of. lard oil fatty acidsadditive of Example 1 including such compositions containing. neutral barium sulfonates and: basic calcium sulfonates was; evaluated according. to the procedure. of Example I.

The neutral barium sulfonate waswprepare'd' by treating a basic barium sul'fonate witlirenough acid oil to neutralize that. the; onset. of staining by, sulfur-chlorinatedalpha-pinene is not retarded: but further the excess basicity. The basic barium sulfonate was oleum in the manner described in Example I.;. The sludge-free and blown acid oil was neutralized directly sulfonate.

The basic calcium sulfonate was prepared in the same manner as the basic barium sulfonate described above except that neutralization'was carried out with calcium hydroxide.

sulfonate and 0.53 per cent calcium hydroxide.

When a mineral oil composition containing 2 per cent of the additive and noinhibitor was used in thetest,

the metal panel showed a stain after days and a strong stain after days. When 0.83 per cent of neutral barium sulfonatewas added to the composition, a stain Q appeared after 7 days and a moderately. strong stain was observed after 30 days. while at a concentration of 2.06 per cent, a stain appeared after 12-days and was. moder-.

ately strong after v30 days. With a concentration'of 1 per cent of the additive and no inhibitor, a stain appeared after 15 days and strong stain was observed after 30', days. When neutral barium sulfonate was added tofthe composition in a concentration of 0.83 per cent, a stain appeared after 7 days and a very. light stain was observed after 30 days while at a concentration of 2.06per cent, a stain appeared after 12 days and stained patches were observed after 30 days.

When compositions containing 2 per cent of the addi V tive and basic calcium sulfonate in a concentrationof 0.21 per cent were usedin the test, a stain appeared after '7 days and a light stain was, observed after 30 days while a concentration of 1.'13 producedastain at 12 days,

and stained patches were observed after 30 days. With an additive concentration of l'per cent and basic calcium sulfonate at a concentration of. 0.21 per cent, a stain appeared after 12 days and a light stain was observed after 30 days while at a concentrationof 1.13 per cent;

a stain appeared after19 days, and sparse stained patches were observed after 30 days. ,7 V V V The results show that the peculiar advantages demonstrated in Examples .1, Hand III andinthisexample of basic barium sulfonate as an inhibitorof the corrosive ness of oil compositions containingsulfur-chlorinated:

pinene type additives do not resideseparately either in the barium sulfonate or the basicity ofthe excess alkaas shown in the above results, even at .a 'grossconcem tration of 2.06 per cent neutral barium sulfonate is a poorer inhibitor than 0.1 per cent basic barium sulfonateQ Basic calcium sulfonate wasused at a concentration of 1.13 per cent which is equivalent to 0.1 percent of the basic barium sulfonate preparation of Example I in basicity, and at a concentration of 0.21 per cent, equivalent in calcium sulfonate'to the barium sulfonate of'the basic barium sulfonate-at 0.1 per cent concentration. Here too, the basic barium sulfonate. is the ,better'inhibitor. In Example I, panels in contact with-additive-containing oil inhibited by only 0.1 per cent gross concentration of basic barium sulfonate were clean and bright" at the end of 60 days, whereasin these tests neither the The preparation contained 23.1 per cent basic calcium sulfonate,- comprising 22.6 percent calcium neutralbarium sulfonate nor the basic calcium sulfonate tokeeppanels free from stain for. as long as were able 30 days. a

Example V sulfonates on turbidity ofimineral oilcompo sitions'con- ,taining sulfurchlorinatedpinene type additives.

Inthe tests," basic bariumf'sulfonate in variousconcenfltrations was added to jrnineral oilicompo'sitionscontainlengths ofitime and then were; shaken vigorously' toi disscattering,flthe' less the turbidity.

' t The basicbariumfisulfonate inhibitor wa ample Theresult'sfare. tabulated below; I a

p 2%Additive x=..%'ruru1dit v 30 1% Additive A: Turbidity 1%;Additive 1B: Turbidity i type additives. V

Iclaim:

' a 1. Cutting oil-compositions of improved'corrosion and turbidity'inhibitingpropertieswhich consist essentially .of. 4O mineral. oil and asulfur-chlorinated pineneiadditive .to Y

which has been; addedibasic barium mahogany-petroleum u sulfonategin, an amount sufiicient to inhibit corrosion; and I turbidity. Y

being'not m rsm'an about 2 weight-per cent; tof'which based'on-the-composition.

1 amount suflicient fto inhibit the ,corros'iveness". and turbidity of cutting oil' compositions'which consist -es'senditive, the amount of.'sulfur chlorinatedpinene additive 5 Tests were'm ade to determine theefiect of basic barium" 7' with excess barium hydroxlde to produce a preparation s I having a base number of 12 mgms. of KOH pergram and containing 15.8 per cent basic barium sulfonate. On, 5 treatment with enough acid oil to neutralize the excess. basicity, the resulting neutral barium petroleum s'ulfonate v "u o t contained 1.76 per cent barium and 12.2 per cent barium mg arm 5 s ofsulfur chlorinated type addmves The oil solutions were. allowed-t stand; for various perse the suspended matter uniformly." 'IhejZturbidity or, each: solution was measured witha-I Iellige turbidimeterg" The light scattered by the solution ofniaximum turbidity. j in each group was taken as 100*pierfcent ai1d the other solutions were evaluated by comparison; .ithe l less.

amp er; The sulfur-chlorinated pinene' type additiVeJA wasthatof 'Example 'lfand additive Bjwas 'that of Ex--.

V results clearlyshow the inhibitingfifiect barium-sulfonate on thejtormation of turbidity in rniner'a'lf' :1 Ioil compositions containing; sulfur-chlorinated pinene' 2, Cutting oil compositions of improvedcorrosion and turbidity inhibiting properties whichconsist..'essentially= of mineral oil and a sulfur-chlorinated-.pinene .additiye, the amount of sulfur-chlorinated pinene additive present] has. been added .Lbas ic bariumv mahogany. petroleum, sul-. fonate in an amount of: about 0.03to 0.-6weiglht.per een 7 ;dit ivewhich comprises addingto the clittiiigjoilcornpo v sitlon; basic, barium mahogany petroleum -sulfo natein an 4. The memes hr inhibiting" the cohesiveness and tur- T tially of mineral oily-and a sulfur chlorinated pineneadg Referencesfcitedginitlie file orthisfl atnt 

1. CUTTING OIL COMPOSITIONS OF IMPROVED CORROSION AND TURBIDITY INHIBITING PROPERTIES WHICH CONSIST ESSENTIALLY OF MINERAL OIL AND A SULFUR-CHLORINATED PINENE ADDITIVE TO WHICH HAS BEEN ADDED BASIC BARIUM MAHOGANY PETROLEUM SULFONATE IN AN AMOUNT SUFFICIENT TO INHIBIT CORROSION AND TURBIDITY. 